Waterless dip dye composition and method of use thereof for synthetic articles

ABSTRACT

A waterless dip dye composition for non-textile and general-utility articles comprises an aromatic ester of the formula ArCOOR 2 , ArCOO--R 1  --OOCAr or (ArCOO) z  --R 3 , wherein R 1  is alkylene of 2-8 carbon atoms or polyoxyalkylene of the formula --C r  H 2r  (OC r  H 2r ) s , in which r is 2 or 3 and s is 1 to 15; R 2  is substituted or unsubstituted alkyl or alkenyl of 8-30 carbon atoms; R 3  is the residue of a polyhydric alcohol having z hydroxyl groups; Ar is substituted or unsubstituted mono- or bicyclic aryl of up to 15 carbon atoms and z is 3-6, admixed with at least 0.5% by weight of a dyeing assistant agent and an organic colorant. 
     A process for coloring non-textile and general-utility articles, fabricated from polyester, polyamide, polyurethane, acrylic, halogenated polyolefin or epoxy plastic, comprises exposing an article to the foregoing compositions, maintained at a temperature from about 100° C. to the temperature at which the plastic degrades, for a time adequate to achieve the desired degree of coloration.

REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of Ser. No. 06/574,953, filed Jan. 30,1984, now abandoned, which is a continuation-in-part of Ser. No.06/440,567, filed Nov. 10, 1982, now abandoned.

Wilson, U.S. Pat. No. 4,529,405 discloses waterless dye compositions,based on bisterephthalate diesters of alkylphenoxypolyoxyethanol and anorganic colorant.

Wilson, U.S. Pat. No. 4,608,056 discloses waterless dye composition,based on an aromatic polyester of the formula C₆ H_(z') (COOR₁)_(z),wherein R₁ is higher alkyl, z is 3, 4, 5 or 6 and z' is 6-z.

Wilson, U.S. Pat. No. 4,581,035 discloses a waterless dye composition,comprising a triglyceride and an organic solvent.

TECHNICAL FIELD

This invention relates to waterless compositions, particularly adaptedfor immersion coloring of plastic articles, intended for non-texile orgeneral-utility use.

BACKGROUND ART

The use of a glycol ether or glycol ester in a dyeing composition hasbeen disclosed, for example, in the following U.S. Pat. Nos.:

    ______________________________________                                        1,891,520           Bowley                                                    1,927,145           Whitehead                                                 1,977,345           Moore et al.                                              2,537,177           Woodruff                                                  2,723,899           Toulmin, Jr.                                              3,009,760           Lenz et al.                                               3,607,358           Dangl et al.                                              3,635,652           Streck                                                    4,047,889           Hermes                                                    4,055,971           Hermes                                                    4,115,054           Hermes                                                    ______________________________________                                    

References disclosing the use of glycols or glycerol as media for dyeingcompositions include U.S. Pat. Nos.:

    ______________________________________                                        2,302,760           Goodman, Jr.                                              2,320,426           Goodman, Jr.                                              2,882,119           Laucius et al.                                            3,241,906           Smith et al.                                              3,901,648           Arbaud                                                    4,245,991           Haddad et al.                                             ______________________________________                                    

Popp et al. (U.S. Pat. No. 3,864,077), have proposed a non-aqueousdyestuff composition, containing a water-soluble or water-dispersibledyestuff, a lower dialkyl phthalate, a dispersing agent andtetrachloroethylene or other halogenated hydrocarbon. The dyeing processappears to require either extended immersion in the dyebath or heattreatment after dyeing.

Hermes (U.S. Pat. No. 3,943,105) has proposed using glycols orpolyhydric alcohols in a process for treating polyester with anultraviolet absorber.

Hermes, in U.S. Pat. No. 3,530,214, has disclosed a process for heatsetting of textiles, wherein a fabric web of synthetic fibers is treatedin a heated liquid bath of a polyhydric alcohol, alkylene carbonate ormixture thereof.

Inclusion of lower phthalates in lubricants or other textile-treatingcompositions is disclosed by Jaeger (U.S. Pat. No. 2,212,369), Brennanet al. (U.S. Pat. No. 2,882,231) and Iyengar et al. (U.S. Pat. No.3,853,607).

Of these, the Hermes '889, '971 and '054 references appear of mostinterest with respect to clean, economically feasible waterless dyeing,particularly of textiles.

The use of ethoxylated materials for coloring of objects has beendisclosed by Lenz et al. (U.S. Pat. No. 3,362,779) and Kressner et al.(U.S. Pat. No. 4,332,587).

Compositions containing esterified derivatives of a Diels-Alder adductof linoleic acid and acrylic acid, intended for use in varioustextile-treating compositions, have been disclosed by Wilson, in U.S.Pat. Nos. 4,293,305, and 4,394,126, incorporated herein by reference.

Although a variety of solvent systems have been suggested for dyeing ofarticles in waterless systems, none presently available provides rapid,failure-free dyeings, which are done without producing obnoxiouseffluents or otherwise being unacceptable from a commercial viewpoint.

It is object of this invention to provide a composition for waterlessimmersion coloring of plastic articles, intended for non-texile andgeneral-utility purposes. Such articles include, but are not limited toplastic tubing and pipe, plastic coated wire, ropes, polyester andpolyamide chips, metals coated with synthetic resins, flowers made ofsynthetic resins, synthetic resin films, toys, synthetic resinconstructions used in cars and planes, housings for pencils and pens,kitchen utensils and telephones.

It is a further object of this invention to provide a method for rapidwaterless coloring of non-texile and general-utility articles. Yetanother object of this invention is to provide an apparatus suitable forwaterless coloring of articles made from plastics.

DISCLOSURE OF INVENTION

In one aspect, this invention relates to a waterless dip dye compositionfor non-textile and general-utility articles, comprising an aromaticester of the formula ArCOOR₂, ArCOO--R₁ --OOCAr or (ArCOO)_(z) --R₃,wherein R₁ is alkylene of 2-8 carbon atoms or polyoxyalkylene of theformula --C_(r) H_(2r) (OC_(r) H_(2r))_(s), in which r is 2 or 3 and sis 1 to 15; R₂ is substituted or unsubstituted alkyl or alkenyl of 8-30carbon atoms; R₃ is the residue of a polyhydric alcohol having zhydroxyl groups; Ar is substituted or unsubstituted mono or bicyclicaryl of up to 15 carbon atoms and z is 3-6, admixed with at least 0.5%by weight of a dyeing assistant composition and an organic colorant.

In another aspect, this invention relates to a waterless dip dyecomposition for non-textile and general-utility articles, comprising athermally-stable, high boiling, non-smoking organic solvent vehicle,free of glycols, glycol ethers, lower alkyl phthalates of dialkylcarbonates, admixed with at least 0.5% by weight of a dyeing assistantagent and an organic colorant.

In a further aspect, this invention relates to a process for waterlesscoloration of non-textile, general utility articles, fabricated from aplastic material, comprising exposing an article to the foregoingcompositions, maintained at a temperature from about 100° C. to thetemperature at which the plastic degrades, for a time adequate toachieve the desired degree of coloration.

"Aromatic ester," as used in the specification and claims, means anester formed by reaction between a mono-, di- or polyhydric alcohol andan aromatic acid, so as to accomplish complete esterification of allhydroxyl functions therein. Compounds within this class include estersof the formula ArCOOR₂, wherein Ar is substituted or unsubstituted mono-or bicyclic aryl of up to 15 carbon atoms and R₂ is substituted orunsubstituted alkyl or alkenyl of 8-30 carbon atoms. Also includedwithin the definition of aromatic esters are those of the formulaAR--COO--R₁ --OOCAr, wherein AR is as above and R₁ is alkylene of 2-8carbon atoms or polyoxyalkylene of the formula --C_(r) H_(2r) (O--C_(r)H_(2r))_(s), in which r is 2 or 3 and s is 1 to 15.

Accordingly, aromatic esters used in this aspect of the inventioninclude, but are not limited to, esters of benzoic, toluic,dimethylbenzoic, trimethylbenzoic, naphthoic, butylbenzoic and similaracids.

In the practice of this invention, the foregoing types of esters willpreferably be used in combination with a cycloaliphatic diester of theformula ##STR1## wherein R is substituted or unsubstituted straight orbranched chain alkyl of 4-20 carbon atoms, polyoxyalkylene of theformula HO(C_(x) H_(y) O)_(n) C_(x) H_(y) -- or phosphatedpolyoxyalkylene of the formula

    (HO).sub.2 P(═O)O(C.sub.x H.sub.2x O).sub.n C.sub.x H.sub.2x

or a salt thereof, wherein (C_(x) H_(2x) O)_(n) is (CH₂ CH₂ O)_(n), (C₃H₆ O)_(n) or (CH₂ CH₂ O)_(p) --(C₃ H₆ O)_(q) and n is 2-22. Othercycloaliphatic diester compounds which can be used are those wherein Ris ArCOO(CH₂ CH₂ O)_(n) CH₂ CH₂ --, ArCOO(C₃ H₆ O)_(n) C₃ H₆ --,ArCOO(C₂ H₄ O)_(p) (C₃ H₆ O)_(q) C₃ H₆ -- or ArCOO(C₃ H₆ O)_(p) (C₂ H₄O)_(q) C₂ H₄ -- and n, p, q and Ar are as above. Preferred compositionsof this invention will contain at least 5% by weight of this type ofcycloaliphatic diester.

Preferred aromatic esters employed in the practice of this inventioninclude those based on tri- or polyhydric alcohols, such as glycerol,trimethylolpropane, pentaerythritol, diglycerol, sorbitol, mannitol, andthe like. The aromatic acids used for esterification are as above. Whenesters of this type are used, it has been found that entirely acceptabledyeings can be obtained, without the use of a cycloaliphatic diester,required for good results in combination with aromatic esters of mono-and dihydric alcohols. Aromatic esters of tri- and polyhydric alcoholscan be represented by the formula (ArCOO)_(z) --R₃, wherein R₃ is theresidue of a polyhydric alcohol having z hydroxyl groups and z is 3-6.

When aromatic diesters of dihydric alcohols are used, alkylene (R₁) canbe ethylene, propylene, hexylene, 2,2-dimethyltrimethylene, butylene,heptamethylene and octylene, including various isomers thereof.

Polyoxyalkylene diesters include those derived from polyethylene glycolor polypropylene glycol.

In the case of aromatic esters of monohydric alcohols, alkyl (R₂) can beoctyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, stearyl and alkenylcan be any corresponding monounsaturated function, e.g., oleyl.

Preferred among aromatic esters of mono-or dihydric alcohols are thosewherein:

(a) Ar is phenyl,

(b) Ar is tolyl,

(c) R₁ is ethylene or propylene, including each of (a) and (b),

(d) R₁ is ethyleneoxyethylene or propyleneoxypropylene, including eachof (a) and (b),

(e) R₁ is polyoxypropylene of molecular weight 200-250, including eachof (a) and (b), and

(f) R₂ is decyl, dodecyl, hexadecyl, tridecyl, octadecyl or oleyl,including each of (a) and (b).

Contemplated equivalents of the aromatic esters described above includeesters of benzyl alcohol and substituted or unsubstituted aromatic acidsof 6 or more carbon atoms, or substituted or unsubstituted aliphaticacids of 8 or more carbon atoms, including but not limited to, benzyllaurate, benzyl pelargonate, benzyl octoate, benzyl palmitate, benzylstearate, benzyl oleate, benzyl hydroxystearate or benzyl benzoate. Itwill be understood that esters of substituted benzyl alcohols can alsobe used.

Preferred aromatic esters based on trihydric or polyhydric alcohols arethose of glycerol, trimethylolpropane or pentaerythritol. Most preferredare benzoate or toluate esters. It will be understood that mixtures ofaromatic acids can be used to prepare any of the aromatic esters used inthe practice of this invention.

The dibasic cycloaliphatic acid employed in making the compositions ofthis invention is a Diels-Alder adduct of acrylic acid and linoleic acidand can be prepared as described by Ward in U.S. Pat. No. 3,753,968. Thediacid has the formula ##STR2## and therefore is a mixture of (5 and6)-carboxy-4-hexyl-2-cyclohexene-1-octanoic acids. The diacid isavailable commercially from Westvaco, designated as "Diacid 1550".

Preparation of adducts from conjugated octadecadienoic acid andunsaturated acids and/or their hydrogenation has also been described byTeeter et al. J. Org. Chem., vol. 22 (1957) at 512-514, Ward in U.S.Pat. No. 3,988,476 and Ward et al in U.S. Pat. No. 3,981,682.

The preparation of esters from the C₂₁ diacid adduct was reported byWard et al, J. Amer. Oil Chemists' Soc., vol. 57 (1957) at 219-224.Ethoxylated esters containing 4-119 ethylene oxide units are said to beeffective lime soap dispersants. The alkyl esters are reported as beinguseful in lubricant applications, including users as textile lubricantsand plasticizers for PVC.

The diacid can be esterified with alcohols using, for example, acidiccatalysts such as p-toluenesulfonic acid, methanesulfonic acid orsulfuric acid. During the esterification, the reaction mixture ispreferably also treated with a decolorizing agent, e.g., carbon or clay.

The diacid is reduced following esterification to a saturated compoundcycle. A nickel catalyst such as Raney Nickel, nickel on kieselguhr ornickel on alumina can be used. The required amount varies up to 5-10% byweight of the ester.

Hydrogenation is carried out after esterification to prevent nickel fromcomplexing with the free acid. Other catalysts, e.g., platinum orrhodium, avoid this problem, but are prohibitive in cost. The catalystcan be removed by filtration through a plate and frame filter press. Theproduct is the resulting filtrate.

Polyoxyalkylene diesters are prepared by reaction of the diacid, in thepresence of an alkaline catalyst, with ethylene or propylene oxide.Reaction will occur at both acid sites. Addition of ethylene oxide isallowed to continue until the product becomes at least dispersible or,preferably, soluble in water. This will correspond to addition of atotal of 5-25 ethylene oxide units. The product obtained using ethyleneoxide has a structure before hydrogenation represented by the formula:##STR3##

The phosphorylated product is readily obtained by reaction withphosphorus pentoxide. The saturated diester can be obtained bynickel-catalyzed hydrogenation.

In the case of the phosphorylated derivative, hydrogenation shouldprecede phosphorylation. The phosphorylated derivatives can be convertedto salts thereof by reaction with a metal hydroxide. Sodium andpotassium salts are preferred.

Compounds in which R is ArCOO(CH₂ CH₂ O)_(n) CH₂ CH₂ --, etc. areobtained by treating polyoxyalkylene intermediates with an aromaticacid, e.g., benzoic, toluic or metallic acid, usually with an acidiccatalyst. Hydrogenation of the double bond in the cycloaliphatic ringcan be done before or after esterification with the aromatic acid.

Representative of substituted alkyl R which may be used in the productsof this invention are butoxybutyl, 10-hydroxystearyl, 10-hydroxydecyl,10-halostearyl, ω-alkanoyloxyalkyl or the like.

Preferred diesters for use in accordance with the principles of theinvention are those wherein:

(a) R is straight or branched chain alkyl of 4-20 carbon atoms,

(b) R is 2-ethylhexyl, lauryl or stearyl,

(c) R is HO(CH₂ CH₂ O)_(n) CH₂ CH₂ --,

(d) R is HO(C₃ H₆ O)_(n) C₃ H₆ --,

(e) R is HO(C₂ H₄ O)_(p) (C₃ H₆ O)_(q) C₃ H₆ --,

(f) R is (HO)₂ P═O(OCH₂ CH₂)_(n) OCH₂ CH₂ -- or a salt thereof,

(g) R is C₆ H₅ CO(OC₂ H₄)_(n) OC₂ H₄ --,

(h) R is CH₃ C₆ H₄ CO(OC₂ H₄)_(n) OC₂ H₄ --

(i) R is C₆ H₅ CO(OC₃ H₆)_(n) OC₃ H₆ --, and

(j) R is CH₃ C₆ H₄ CO(OC₃ H₆)_(n) OC₃ H₆ --.

"Dyeing assistant agent," as used in the specification and claims,includes alkoxylated alkylphenols and their esters, alkoxylated castoroil compounds, alkoxylated hydrogenated castor oil compounds,alkoxylated primary alkanols, salts of phosphated alkoxylated primaryalkanols and mixtures thereof.

The amount of dyeing assistant agent, employed in the compositions ofthis invention, is at least about 0.5% by weight of the composition.However, it is preferred that the compositions contain at least 5%, morepreferably up to about 80% by weight, of dyeing assistant agent.Preferred compositions can also contain 60-80% by weight of dyeingassistant agent.

Preferred dyeing assistant agents are alkoxylated alkylphenols and theiresters. These are compounds of the formula

    C.sub.a H.sub.2a+1 --C.sub.6 H.sub.4 --O(C.sub.x H.sub.2x O).sub.b R",

wherein a is 1-12; b is 1-24; R" is H, aroyl of mono- or bicyclicaromatic acids of up to 15 carbon atoms or substituted or unsubstitutedalkanoyl of 8-30 carbon atoms. Accordingly, exemplary dyeing assistantagents include ethoxylated and propoxylated alkyl phenols andcorre-sponding esters, such as the laurate, myristate, palmitate,coconate, oleate, stearate, isostearate, benzoate and toluate esters.Preferred alkylphenols are nonylphenol, octyphenol, and dodecylphenol.

It will be understood that the alkylphenols and the acids used toesterify the alkoxylated alkylphenols can include mixtures.

Most preferably, the alkoxylated alkylphenols will be ethoxylatedderivatives, having 5-10 ethylene oxide units.

Preferred dyeing assistant agent will be those wherein:

(a) R" is alkanoyl of 12-18 carbon atoms, including mixtures thereof;

(b) R" is n--C₁₇ H₃₃ CO;

(c) R"is n--C₁₇ H₃₅ CO;

(d) R" is iso--C₁₇ H₃₅ CO;

(e) R" is benzoyl;

(f) R" is n--C₁₁ H₂₃ CO;

(g) R" is H;

(h) a is 5-10, including each of (a)-(g);

(i) b is 6-15, including each of (a)-(h);

(j) b is 8-11, including mixtures thereof and including each of (a)-(h);

(k) a is 9, b is 8-10 and R" is n--C₁₁ H₂₃ CO;

(l) a is 9, b is 6-10 and R" is H and

(m) x is 2, including each of (a)-(l).

Alkoxylated castor oil used as an optional additive in the compositionsof this invention will contain 15-100 oxyalkylene units, preferably40-85 oxyethylene units. The hydrogenated castor oil derivatives willcontain 5-200 oxyalkylene units, preferably 20-30 oxyethylene units.These types of materials can be purchased from ICI America andWhitestone Chemical Co.

It surprisingly appears that the vehicles for the dye compositions ofthis invention essentially act as heat transfer agents and that, inaddition to the specifically disclosed vehicles, any vehicle can be usedfor waterless dyeing of nontextile and general-utility articles,provided that the vehicle is high boiling, thermally stable above atleast 100° C. and non-smoking and is free of glycols, glycol ethers,lower alkyl phthalates or dialkyl carbonates. The vehicles are also freeof halogenated hydrocarbons or polyhydric alcohols.

It is preferred that compositions, stable above 120° C., more preferablythose stable above 140° C., be selected.

The types of plastic materials which can be colored using thecompositions and method of this invention include, but are not limitedto, polyesters, polyamides, polyurethanes, acrylics, halogenatedpolyolefins and epoxy plastics.

Polyester articles include those made from poly(alkyleneterephthalates), such as poly(ethylene terephthalate), or polyestersmade from cyclohexanedimethanol. Typical of polyester articles are chipsof polyester resin, polyester coating on wires or metal, flowers,polyester film, toys, glass-filled polyester articles, includingstyrenated polyester articles, components of cars and planes andhousings for pencils and pens.

Polyamides particularly contemplated as substrates in the practice ofthis invention include those known as nylons, 6; 6,6 or 6,10. Articleswhich can be colored in accordance with the invention include the sametypes of articles as for polyesters, as well as ropes.

Acrylic plastics, contemplated within the scope of this inventioninclude straight acrylics, such as polyacrylonitrile, and modacrylics.The latter are copolymers of acrylonitrile or methacrylonitrile,generally with vinyl chloride or vinylidene chloride. Also includedwithin the classification of acrylics are high impact resins, whethercomprising blends or graft copolyers, such as are commonly identified asABS (acrylonitrile, butadiene, styrene resins). Articles made of thesetypes of resins include resin chips, coatings on metal or wire,telephones, toys, impact-resistant moldings for cars and planes,housings for pencils and pens and kitchen utensils.

Polyurethanes include a myriad of compositions, made by reaction, forexample, between glycols and organic di- or polyisocyanates. Among theglycols, used to make polyurethanes, are simple glycols, such as thealkylene glycols, and polymeric glycols, including polyether andpolyester glycols. Articles containing polyurethane, used in articlesgenerally as above, particularly including toys and moldings andextrusions for automobiles and aircraft.

Halogenated polyolefins include polyvinyl chloride and polyvinylidenechloride, including their copolymers. Also included among halogenatedpolyolefins are post-chlorinated materials, such as chlorinatedpolyethylene (CPE) and post-chlorinated PVC. These resins are commonlyemployed in pipes and tubing, for above and below ground installation,for wire and metal coating, for building sidings and for films.

Epoxy resins are the reaction products of a polyglycidyl ether and acuring agent, particularly a polyamine. These resins often have veryhigh impact resistance and will, accordingly, be used in fiberglassfilled compositions for boats and automobiles.

In some instances, the foregoing types of plastics can be blended withnatual or synthetic cellulosic materials and colored according to thisinvention.

"Organic colorant," as used in the specification and claims, includesboth dyes and pigments of any structure. Normally, the dyes or pigmentswhich are employed need not be soluble in water. Therefore, such dyesand pigments will not usually contain water-solubilizing functions, suchas a plurality of sulfonic acid groups. The dyes or pigments used in thepractice of this invention generally will be chosen from amongwater-insoluble dyes, which are also known as disperse dyes. Includedwithin this class of dyes, which can be used on fibers such as celluloseacetate, polyamides or polyesters, from any kind of dyeing medium arecolors having azo, azomethine, nitroarene and anthraquinone structures.It is to be understood that the dyes useful in the practice of thisinvention are not limited to these classes of compounds.

The dyes or pigments used in the practice of this invention may beidentified by their chemical names, for example:

3-nitro-N⁴ -phenylsulfanilanilide, a yellow dye;p-[p-(phenylazo)phenylazo]phenol, a red-yellow dye; ethyl4-hydroxy-1-anthraquinonecarbamate, an orange dye;1-amino-4-hydroxyanthraquinone, a red dye;1-amino-2-bromo-4-hydroxyanthraquinone, a red-blue dye or4,5-diaminochrysazin, a blue dye.

Alternatively, the dyes may be identified by standard chemicaltextbooks, such as "The Color Index," third edition, The Society of Dyesand Colours and The American Association of Textile Chemists andColorists (1971). This type of handbook correlates dye structure withtrade names. Typical of colorants thus identified, which dyes can beused in the practice of this invention, are Solvent Orange 20; Acid Blue83 (C.I. 42660); Acid Blue 59 (C.I. 50315); Direct Blue 86 (C.I. 74810);Direct Red 81 (C.I. 28160) and Acid Yellow 36 (C.I. 13065).

Cationic dyestufffs can also be used in the practice of this invention,for example, Rhodamine 6G, Rhodamine B, Rhoduline Blue 6G and MethyleneBlue BB.

Similarly, metallized azo dyestuffs can be employed in the practice ofthis invention. Representative azo dyestuffs which can be used are Co,Ni, Cu or Cr complexes of coupling products of 2-amino-4-nitrophenol andresorcinol; 2-amino-4-chloro-5-nitrophenol and acetoacetanilide;dianisidine and 3-hydroxy-2-naphthanilide;2-amino-4-chloro-5-nitrophenol and 2-aminonaphthalene or the like.

It will further be understood that other textile-treating agents, suchas optical brighteners, e.g., styrylnaphthoxazole compounds, can beapplied, along with dyes or pigments.

The dyes or pigments can be used in any form, that is, as presscake oras dried pressed dye. The addition of dispersing agents is optional.Alternatively, the dyes or pigments can be added to the dye bath in asolvent or dispersing medium, compatible with the dye bath. It isconvenient and preferred, in the practice of this invention, to useadditive-free, solid disperse dyes.

It has been found, in accordance with this invention that articles canbe dyed or colored very rapidly and very homogeneously. Normally,immersion in the dye bath for as little as 30 seconds at 160° C. willgive significant coloration. However, for even faster results, thedyeings can be done at 180°-200° C. or higher. Employing thecompositions of this invention at 200° C. or more does not result insmoking or pollution of the processing plant, which is a problem whenethylene glycol or diethylene glycol are the dyeing solvents. Inpractice, it is feasible to use a temperature, up to that at which theplastic article will begin to degrade. However, temperatures of120°-235° C., more preferably, 140°-235° C., are recommended.

Although it is preferred to dye the articles being treated by immersionin a bath of the dye composition, the dyes can also be applied byspraying. Then, the sprayed articles should be heated in a bath to atleast 140° C. to complete uptake of the dye into the article.

Whether the article is dyed by immersion or otherwise, the dye articleis normally cleaned with a solvent to remove excess dye. Preferably, thesolvents used for cleaning are chlorinated or fluorinated hydrocarbons.However, highly chlorinated solvents, such as perchloroethylene andtrichloroethylene are preferred when cleaning is to be done in a liquidbath. When vapor-phase cleaning is to be done, a more volatile solvent,particularly a chlorofluorocarbon, such as dichlorodifluoromethane orchlorotrifluoromethane, will be selected. Normally, means will be usedto recover and recycle the cleaning solvent, rather than discharging itto the atmosphere.

A further advantage of the process of the invention is that it isessentially self-contained and effluent free, that is, little or nomaterial is lost or discharged to the atmosphere.

In the apparatus of this invention, as shown in FIG. 1, the majorcomponents include a dip tank, a dye recovery unit, a solvent cleaningtank, a solvent recovery still and a drier. The dip tank will beprovided with heating means and stirring means, as as to permitcirculation of the dyeing solution within the dip tank and to a dyerecovery unit external thereto.

The dye recovery unit normally includes filtration means for removal ofsolid debris from used dye solutions and distilling and condensing meansfor recovery of the solvent. The purified dye solution can be recycledto the tip tank, with addition of dye or other additives to provide thedesired composition in the dip tank. Alternatively, the purified dyesolution can be stored for later use.

It is preferred, in coloring many types of articles, to provide porousbelt or squeeze roller means, for removal of excess dye solution fromtreated articles. The dye removal means employed at this point will beselected according to the shape and size of the articles being coloredin the dip tank. The dye solution removed at this point can be cycled tothe external recovery unit or can be returned directly to the dip tank.

Articles leaving the squeeze roll or belt station are passed into thesolvent cleaning tank to complete removal of any excess or unadherentdye matter. It is preferred to use a plurality of solvent cleaningtanks. It is also preferred to circulate solvent from the tank throughan external solvent recovery unit, provided with filters to remove solidmaterials and distilling and condensing means for purifying solvent, andto return purified solvent to the system. Dye recovered on the filter oras the distillation residue can be returned to the system for recycle.When a plurality of solvent cleaning tanks are employed, it is preferredto flow solvent countercurrently to the direction in which the articlesbeing treated, are moved.

The final component of the apparatus is the drying means, such as an airdryer, from which articles leaving the system can be inspected andpackaged. Solvent vapors from the hot air dryers can be condensed andreturned to the system.

BRIEF DESCRIPTION OF THE DRAWING

In FIG. 1 is shown an apparatus, suitable for use in accordance with theinvention.

BEST MODE FOR CARRYING OUT THE INVENTION

In a most preferred aspect, the compositions of this invention will bethose wherein the aromatic ester is of the formula (ArCOO)_(z) --R₃, Aris phenyl or tolyl, R₃ is the residue of glycerol, trimethylolpropane orpentaerythritol and the composition contains at least 5% by weight of analkoxylated alkylphenol or an ester thereof. Most preferably, thecompositions will contain at least 5% by weight of a hydrogenatedcycloaliphatic diester, obtained from linoleic acid and acrylic acid,and the organic colorant will be a disperse dye.

A most preferred process in accordance with this invention is onewherein the article being treated is exposed to the foregoingcomposition, maintained at a temperature of 140°-235° C., for a timeadequate to achieve the desired degree of coloration.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention tothe fullest extent. The following specific embodiments are, therefore,to be construed as merely illustrative and no limitative of theremainder of the disclosure in any way whatsoever. In the followingexamples, the temperatures are set forth uncorrected in degrees Celsius.Unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE 1 Preparation of Propylene Glycol Dibenzoate

To a 3-necked flask fitted with stirrer, condenser, receiver,thermometer, nitrogen purge and heating mantle were charged 84 g (1.1mole) of propylene glycol, 244 g (2 moles) of benzoic acid and 0.8 g ofp-toluenesulfonic acid. Air was purged from the flask with nitrogen andthe contents of the flask were heated to 160°-170° C. Water formed bythe reaction was removed continuously. The reaction was continued untilthe product had an acid value below 5 mg KOH/g. The product was cooledand filtered.

Other esters are prepared using the following reactants:

(1) dipropylene glycol and benzoic acid, 1:2 molar ratio

(2) PPG 200 and benzoic acid, 1:2 molar ratio

(3) PPG 500 and benzoic acid, 1:2 molar ratio

(4) glycerol and benzoic acid, 1:3 molar ratio

(5) pentaerythritol and toluic acid, 1:4 molar ratio

(6) trimethylolpropane and mixture of benzoic and toluic acids, 1:3molar ratio.

EXAMPLE 2 Preparation of Polyoxyethylene Nonylphenyl Laurate

To a three-necked flask fitted out as in Example 1 was charged 750 g(1.1 moles) of polyoxyethylated nonylphenol (9.5 moles of oxyethylene,NP 9.5), 208 g (1 mole) of lauric acid and 2.4 g of p-toluenesulfonicacid. Air was purged from the flask with nitrogen and the mixture washeated to 160°-170° C. until an acid value below 10 mg/KOH was obtained.The product was cooled and filtered.

Other polyoxyethylene compounds are made in a similar fashion from:

(1) NP 9.5 and coconut fatty acid, 1:1 molar ratio

(2) NP 9.5 and oleic acid, 1:1 molar ratio

(3) NP 9.5 and stearic acid, 1:1 molar ratio

(4) NP 9.5 and benzoic acid, 1:1 molar ratio.

EXAMPLE 3 Preparation of Unsaturated Cycloaliphatic Diester: (R is2-ethylhexyl)

To a three-necked flask fitted with stirrer, thermometer, nitrogenpurge, condenser, side-arm receiver and heating mantle were charged 352g (1 mole) of Diacid 1550, 273 g (2.1 moles) of 2-ethylhexanol, 1.5 g ofp-toluenesulfonic acid and 2 g of decolorizing carbon. Air was purgedfrom the flask with nitrogen and the reaction mixture was stirred andheated to 160°-170° C. for 4-6 hours. Water formed during the reactionwas collected in the side-arm receiver. The reaction was continued untilthe acid value was below 5 mg KOH/g. The catalyst and carbon was removedby filtration. The ester product and 25 grams of nickel on kieselguhrwere charged to a stirred, heated pressure vessel. The mixture washeated to 160°-170° C. and pressurized to 400 psig with hydrogen. Asample was removed after 6-8 hours for determination of the iodinevalue. The reaction was continued until the iodine value was below 0.5 gof iodine/100 g of sample.

The product was cooled to 50° C. and the catalyst was removed byfiltration.

Esters are prepared similarly from:

(1) Diacid 1550 and decyl alcohol, 1:2 molar ratio

(2) Diacid 1550 and tridecyl alcohol, 1:2 molar ratio

(3) Diacid 1550 and Neodol 25 (a mixture of 12-15 carbon alcohols), 1:2molar ratio.

EXAMPLE 4 A. Preparation of Polyoxyethylene Unsaturated CycloaliphaticDiester: (R is HO(CH₂ CH₂ O)_(n) CH₂ CH₂ --)

To a stirred autoclave fitted with heating and cooling coils was charged352 g (1 mole) of Diacid 1550. Catalyst (1.0 g of potassium hydroxide)was charged to the reactor. The temperature was raised to 110° C. andthe reactor was vacuum stripped for 30-60 minutes to remove any residualwater from previous washing of the reactor or from one or more of thecharged reactants or catalyst. The reactor was purged with nitrogen toremove air, evacuated again and purged again with nitrogen. The contentsof the reactor were stirred and heated to 140° C. and 100 g (2.3 moles)of ethylene oxide was added to the reactor. The pressure inside thereactor immediately built up to 30-50 psig. After 30-60 minutes'induction time, an exothermic polymerization reaction (to 150°-160° C.)began. The reaction was accompanied by a pressure drop to zero (0 psig)as the ethylene oxide was consumed. Ethylene oxide was added to thereactor to a total of 660 g (15 moles). The temperature was maintainedat 150°-160° C. by cooling. Addition of ethylene oxide was stopped andthe reaction was allowed to continue for 30 minutes more. The reactorwas cooled to 90°-100° C. and purged twice with nitrogen.

A sample of the product had a hydroxyl value of 110 mg of KOH/g (15moles of ethylene oxide added to the diacid.) The diester was acidifiedwith acetic acid to neutralize the potassium hydroxide catalyst andtreated with 3 g of hydrogen peroxide to bleach and lighten the color ofthe product. The reactor was cooled to 30° C. prior to removing theproduct, which was filtered through filter paper, using a porcelainfilter.

B. Reduction to the Polyoxyethylene Diester

The product of Example 4A and 25 g of nickel on kieselguhr were chargedto a stirred, heated pressure vessel. The mixture was heated to160°-170° C. and pressurized with hydrogen to 400 psig. After 6-8 hours,samples were removed at intervals for determination of the iodine value.The reaction was continued until the iodine value was less than 0.5g/100 g of sample.

EXAMPLE 5 Preparation of Phosphated Polyoxyethylene Diester: (R is (HO)₂P(═O)(OCH₂ --CH₂)_(n) OCH₂ CH₂ --)

Polyoxyethylated (15 moles of ethylene oxide) diacid, obtained as inExample 4B was heated to 50°-60° C., stirred and purged thoroughly withnitrogen to remove air. To about 1015 g (1 mole) of this material wasadded 24 g (0.17 mole) of phosphorus pentoxide. An exothermic reactionbegan immediately, with an exotherm to 85°-95° C. The reaction mixturewas maintained at this temperature by cooling and an additional 24 g(0.17 mole) of phosphorus pentoxide was added. The reaction wascontinued for three hours after all of the phosphorus pentoxide wasadded. The reactor was cooled to 50° C. prior to removal of a sample.The acid value of the product was 32 mg KOH/g, indicating that thereaction was complete. The batch was bleached at 85°-95° C. with 5 g ofhydrogen peroxide, cooled to 30° C. and filtered.

EXAMPLE 6 Aroylpolyoxyethylene Cycloaliphatic Diester

An aroylpolyoxyethylene cycloaliphatic diester was synthesized in atwo-liter autoclave fitted with nitrogen purge, condenser and receiverfor the removal of by-product water. Charge weights were:

    ______________________________________                                        510.0      g.          Diacid 1550                                            2.0        g.          flake caustic                                          636.0      g.          ethylene oxide                                         ______________________________________                                    

After purging the system with nitrogen, Diacid 1550 and caustic wereheated to 130° C. Ethylene oxide was added over a four-hour period,during which the temperature was kept at 150°-165° C. The resultingethoxylated product was cooled to 90° C. for removal of a sample. The(by hydroxyl value) was 139. To this intermediate was added:

    ______________________________________                                        3.5      g.        acetic acid (glacial)                                      7.5      g.        methanesulfonic acid (70%)                                 340.0    g.        benzoic acid                                               ______________________________________                                    

After purging with nitrogen, the temperature of the mixture was raisedto and held at 165°-170° C. until the acid value was less than 5 mg KOHper gram. The theoretical amount of water was removed during thereaction and collected in the receiver. The sample was cooled andfiltered.

The filtered product was hydrogenated in a two-liter autoclave:

    ______________________________________                                        1000.0    g         ethoxylated product, above                                50.0      g         Raney nickel                                              QS                  hydrogen                                                  ______________________________________                                    

The reduction was run at 100°-125° C. and 200-250 psig until hydrogenconsumption ceased. The product was cooled and filtered.

A propoxylated dibenzoate ester was prepared in a similar fashion.

EXAMPLE 7

A representative benzyl ester was prepared from:

    ______________________________________                                        227.0    g         benzyl alcohol                                             400.0    g         lauric acid                                                2.24     g         methanesulfonic acid (70%)                                 0.6      g         hypophosphorous acid (50%)                                 ______________________________________                                    

The resulting mixture was heated and held at 165°-175° C. until thetheoretical amount (37 g) of water was removed. Approximately 580 gramsof benzyl laurate were recovered.

The benzyl esters of pelargonic, octanoic, palmitic, stearic, oleic andhydroxystearic acids were prepared in a similar fashion.

EXAMPLE 8

Ethoxylated castor and hydrogenated castor oils were prepared as inExample 4. Ethylene oxide adds to the hydroxyl group of castor oil.

EXAMPLE 9

A waterless dyeing composition was prepared from glyceryl tribenzoate(Velsicol Chemical Corp.) and nonylphenol 7 (7 oxyethylene units, UnionCarbide Corp.) in 20:80 weight ratio, containing 1 gram/liter ofpresscake blue dye.

This composition was kept at 180° C. and stirred while afiberglass-polyester composite was immersed therein for one minute. Thesample was removed, washed in perchloroethylene and dried. The samplewas homogeneously colored with good dye fixation. There was little or nosmoking during the coloring operation.

EXAMPLE 10

Compositions similar to that of Example 9 were used to color thefollowing articles, under the conditions indicated:

(a)

180° C., 2 min

nylon ring

electrical cord

screen wire

nylon beads

nylon cord

(b)

180° C. for 3 min

PVC pipe

(c)

180° C. for 5 min

polyester chunk

In each case, the article was colored evenly. No splotches wereobserved. The products were cleaned easily with perchloroethylene.

EXAMPLE 11

(a) Dye solution comprising ethylene glycol, containing 1 gram/liter ofpure presscake blue dye, was heated to 180° C. with constant stirring.The solution began to smoke at about 107° C. Smoking became verytroublesome at 125° C. and even worse at 180° C.

Into the solution at 180° C. was immersed a six-inch piece of polyesterzipper. After one minute's immersion, the zipper was removed, cooled inair and cleaned in perchloroethylene solution, to remove residual dyesolution. The zipper was difficult to clean. The zipper was unevenlycolored and had many splotches.

(b) A similar experiment was done, using diethylene glycol as solvent.The dyed product was unevenly dyed and had many splotches.

These experiments demonstrate that use of glycol solvents areunacceptable from a pollution standpoint and that unacceptable dyeingsare obtained.

EXAMPLE 12

A 3/16 inch stainless steel tank of 70 gallon capacity containing 520pounds of dip dye solution, as in Examples 9 and 10, at a dye level of0.5 pound of Latyl Blue BCN 356 (crude ground dye) was heated externallyto provide a temperature of 182° C.

A pump was used to circulate material in the dye bath during heating andwhile a polyester zipper about two feet long was immersed in the stirredbath for about 30 seconds. The zipper was removed from the bath andlightly squeezed with a roller to remove excess dye solution. The zipperwas washed in a tank containing a mixture of trichloroethylene andperchloroethylene. After 30 seconds' immersion in the bath, the zipperwas dried in a hot air chamber. The zipper was ready for finalinspection and shipment.

The zipper was rapidly dyed by this method and was pleasant inappearance.

EXAMPLE 13

Dip dye solution is made from the following ingredients, as above:

    ______________________________________                                        parts by weight                                                               ______________________________________                                        40           hydrogenated cycloaliphatic diester                                           with 2-ethylhexyl alcohol (Example 3)                            40           propylene glycol dibenzoate                                      20           POE nonylphenyl laurate (Example 2)                               1           Latyl Blue BCN 356                                               ______________________________________                                    

The dip dye is used as in Examples 9 and 10. Similar results areobtained.

EXAMPLE 14

Dip dye solution is made as above from:

    ______________________________________                                        parts by weight                                                               ______________________________________                                        (a)   20           POE nonylphenol (N.P. 8.5)                                       50           glyceryl tribenzoate                                             30           hydrogenated cycloaliphatic diester                                           of Example 3 (Neodol 25)                                          2           presscake blue                                             (b)   10           hydrogenated cycloaliphatic diester                                           of Example 3 (decyl alcohol)                                     50           diethylene glycol ditoluate                                      50           ethoxylated octylphenol oleate                                    1           presscake yellow dye                                       (c)   50           benzyl benzoate                                                  10           hydrogenated cycoaliphatic diester                                            with 2-ethylhexanol                                              40           ethoxylated dodecylphenol                                        1.5          presscake green dye                                        ______________________________________                                    

The foregoing compositions are used for coloration of general-utilityarticles, with results similar to those obtained above.

The preceding examples can be repeated with similar success bysubstituting the generically or specifically described reactants and/oroperating conditions of this invention for those used in the precedingexamples.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention and, withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

What is claimed is:
 1. A waterless dip dye composition for non-textileand general utility articles, made from plastic, comprising an aromaticester of the formula ArCOOR₂, ArCOO--R₁ --OOCAr or (ArCOO)_(z) --R₃,wherein R₁ is alkylene of 2-8 carbon atoms or polyoxyalkylene of theformula --C_(r) H_(2r) (OC_(r) H_(2r))_(s), in which r is 2 or 3 and sis 1 to 15; R₂ is substituted or unsubstituted alkyl or alkenyl of 8-30carbon atoms; R₃ is the residue of a polyhydric alcohol having zhydroxyl groups; Ar is substituted or unsubstituted mono- or bicyclicaryl of up to 15 carbon atoms and z is 3-6, admixed with at least about0.5% by weight of a dyeing assistant agent and an organic colorant. 2.The composition of claim 1, wherein the dyeing assistant agent is analkoxylated alkylphenol or an ester thereof.
 3. The composition of claim1, wherein the aromatic ester is (ArCOO)_(z) R₃.
 4. The composition ofclaim 3, wherein z is 3 or
 4. 5. The composition of claim 1, wherein thedyeing assistant agent is an alkoxylated alkylphenol or an ester thereofand constitutes at least 5% by weight of the composition.
 6. Thecomposition of claim 1, wherein the dyeing assistant agent is analkoxylated alkylphenol or an ester thereof and constitutes up to about80% by weight of the composition.
 7. The composition of claim 3, whichfurther comprises an alkoxylated castor oil compound, an alkoxylatedhydrogenated castor oil compound, an alkoxylated primary alkanol, a saltof a phosphated alkoxylated primary alkanol or a mixture thereof.
 8. Thecomposition of claim 3, wherein Ar is phenyl or tolyl; R₃ is the residueof glycerine, trimethylolpropane or pentaerythritol and the compositioncontains at least 5% by weight of an alkoxylated alkylphenol or an esterthereof.
 9. The composition of claim 3, wherein Ar is phenyl or tolyl;R₃ is the residue of glycerine, trimethylolpropane or pentaerythritoland the composition contain up to about 80% by weight of an alkoxylatedalkylphenol or an ester thereof.
 10. The composition of claim 1, whereinthe organic colorant is a disperse dye.
 11. A process for coloringnon-textile and general-utility articles, made from plastic, comprisingexposing an article being treated to a composition of claim 1,maintained at a temperature from about 100° C. to the temperature atwhich the plastic degrades, for a time adequate to achieve the desireddegree of coloration.
 12. The process of claim 11, wherein the articleis made from polyester, polyamide, polyurethane, an acrylonitrile ormethacrylonitrile polymer, halogenated polyolefin or epoxy plastic. 13.The process of claim 11, wherein the article is immersed in the coloringcomposition at a temperature of at least 140° C. for at least 1 minute.14. The process of claim 11, wherein the article is sprayed with thecoloring composition and heated in a bath or oven to at least 140° C.15. The process of claim 11, including the further steps of cleaning thecolored article with a halogenated solvent and drying the thus-cleanedarticle.
 16. The process of claim 15, wherein the halogenated solvent isperchloroethylene or trichloroethylene and the halogenated solvent iscollected and recycled to the process.
 17. A process for coloringnon-textile and general-utility articles, made from polyester,polyamide, polyurethane, an acrylonitrile or methacrylonitrile polymer,halogenated polyolefin or epoxy plastic, comprising exposing an articlebeing treated to a waterless coloring composition of claim 3, maintainedat 120°-235° C., for a time adequate to achieve the desired degree ofcoloration.
 18. The process of claim 17, wherein the article is immersedin the coloring composition at a temperature of at least 140° C. for atleast 1 minute.
 19. The process of claim 17, including the further stepsof cleaning the colored article with a halogenated solvent and dryingthe thus-cleaned article.
 20. A process for coloring non-textile andgeneral-utility articles, made from polyester, polyamide, polyurethane,an acrylonitrile or methacrylonitrile polymer, halogenated polyolefin orepoxy plastic, comprising exposing the article being treated to acomposition of claim 8, maintained at a temperature from about 100° C.to the temperature at which the plastic degrades, for a time adequate toachieve the desired degree of coloration.
 21. The process of claim 20,wherein the article is immersed in the coloring composition at atemperature of at least 140° C. for at least one minute.
 22. A processfor coloring non-textile and general-utility articles made from plasticcomprising exposing an article being treated to a waterless liquidcomposition including a high boiling ester, and an organic colorant,maintained at about 120°-235° C. for a time adequate to achieve thedesired degree of coloration.
 23. A process for coloring non-textile andgeneral-utility articles, made from plastic, comprising exposing thearticle being treated to a composition of claim 1, wherein the aromaticester is ArCOOR₂ or ArCOO--R₁ --OOCAr and the composition contains atleast 5% by weight of a cycloaliphatic diester of the formula ##STR4##wherein R is substituted or unsubstituted straight or branched chainalkyl of 4-20 carbon atoms, polyoxyalkylene of the formula R'(OC_(x)H_(2x))_(n) or phosphated polyoxyalkylene of the formula

    (HO).sub.2 P(═O(OC.sub.x H.sub.2x).sub.n OC.sub.x H.sub.2x --

or a salt thereof, wherein (C_(x) H_(2x) O)_(n) is (C₂ H₄ O)_(n) --, (C₃H₆ O)_(n) -- or (C₂ H₄ O)_(p) -- (C₃ H₆ O)_(q) --; R' is H or ArCO; Aris substituted or unsubstituted mono- or bicyclic aryl of up to 15carbon atoms; x is 2 or 3; n is 2-22 and the sum of p+q is n, andmaintaining the composition at a temperature from 100° C. to thetemperature at which the plastic degrades, for a time adequate toachieve the desired degree of coloration.
 24. The process of claim 23,wherein the composition contains at least 5% by weight of dyeingassistant agent selected from an alkoxylated alkylphenol or an esterthereof.
 25. The process of claim 23, wherein the composition containsat least 5% by weight of dyeing assistant agent selected from analkoxylated alkylphenol or an ester thereof and the organic colorant isa disperse dye.
 26. The process of claim 23, wherein the compositionfurther comprises an alkoxylated castor oil compound, an alkoxylatedhydrogenated castor oil compound, an alkoxylated primary alkanol, a saltof a phosphated alkoxylated primary alkanol or a mixture thereof.